SWMOA Annual Symposium

2010 Annual Symposium

Concentrate on Membranes: Inland Treatment Solutions

February 22-25, 2010 y ,

Reverse Osmosis Optimization Improved Rejection Through pH Optimization

Robert Buddy Boysen Separation Processes, Inc.

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Introduction

Few treatment components affect RO performance and treatment costs with as much magnitude as antiscalant selection.

Due to recent developments in antiscalant technology, technology and the price of sulfuric acid acid, many municipalities have considered use of antiscalants that operate at higher pH conditions as a means to reduce sulfuric acid consumption and thereby reduce treatment costs.

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Introduction and Overview

RO Process Description p RO Membrane Chemistry RO Rejection Mechanisms Antiscalants Theoretical RO Performance Impact of pH Change Project Background Full Scale Testing Procedure Results

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Reverse Osmosis Science

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RO Membranes Thin Film Composite Material Example

Gutter Layer Sometimes a gutter layer is applied to act g y pp as an intermediate support. Gutter layer has a looser pore structure than the Selective Layer but much tighter pore structure than the Support Layer

Sealing Layer Thin Layer of highly permeable material that protects the membrane during handling

Selective Layer Thin polyamide coating, 0.5 to 2 microns thick. Very tight pore structure. Essentially defect free is required y q to provide good separation and performance. Microporous Support Layer Consists of Polysulfone cast onto a nonwoven polyester fabric fabric. Flux > 10 Times the Selective Coating, 90% of headloss through the coating. Pores must be small enough to support the coating under high pressure to prevent damage t the Selective Layer. d to th S l ti L Support layer does not separate water from dissolved ions.

Adapted from R.W. Baker Membrane Technology and Applications

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RO Membranes Polyamide Chemistry

O C O C N H H N
x

O C

O C N H C O N H
y

Adapted from FilmTec RO Membranes Technical Manual and Freeman Paper

Surface Charge is Negative Similar Charges Repel Negative. Repel. Lots of functional groups that can contribute electrons to the polymer molecule. Inductive effects can be manipulated by the treatment stream. pH of solution will change membrane surface characteristics (charge).

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RO Membrane Rejection

Rejection Theoretically Complicated: Controlled by many factors: size exclusion, shape factor, charge repulsion, membrane material properties and others. l i b t i l ti d th Many Transport Mechanisms Proposed: Physical Models I l d Ph i l M d l Include: solution diff i l ti diffusion, pore fl flow, preferential f ti l sorption capillary flow and others.

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Antiscalants
Chemistry: hexametaphoshpate. Original Antiscalant: sodium hexametaphoshpate Common antiscalant blends include polyacrylate, polycarboxylate and phosphonate. Other available blends include dendrimers and organophosphates. New Antiscalant Blends can Improve System Performance: p y Operation at elevated p or g pH greater water recovery may be feasible. Operation at increased pH is considered by most facilities due to cost savings associated with decreased sulfuric acid consumption.

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Theoretical Process Impact of pH Change

Membrane Surface Electronegativity Changes: Increased membrane surface electronegativity leads to greater charge repulsion and therefore greater selectivity of the membrane. Component Speciation Changes: Speciation can affect the size/charge of resulting S ff / f molecules. Ex: boron vs. tetraborate Charged O Ch d Organics I i Impacted b pH: t d by H Changing the surface charge of functional groups can i increase repulsion and slow diff i th l i d l diffusion through h the concentration polarization region.

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City of Scottsdale AWT Expansion Project

City f Scottsdale Water Campus AWT R Cit of S tt d l W t C Reverse O Osmosis S t i System

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History
City of Scottsdale Water Campus City Owned Water Resource Management Tool Advanced Municipal Wastewater Treatment Conventional Water Reclamation Plant (WRP) Advanced Water Treatment Plant (AWT)

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Water Campus WRP

Conventional Process: MLE Biological Treatment Process Provides Nitrification De-Nitrification (NO3 less than 8 mg/L) Disk Filters Provide Tertiary Filtration High Quality Effluent (Tubidity typically less than 0.5 ntu)

Secondary y Sludge

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Water Campus AWT

CAP Water

Advanced Water Treatment Process: Chloramination Equalization E li ti Microfiltration

Ammonia Chlorine

Chlorination Vault

From WRP Reservoir B Ammonia Boost Dechlor Vault Reservoir A

Auto Strainers

Auto Strainers

M MF MAW WT

M MF MCA AP

Backwash PS

To WRP

Reverse Osmosis Decarbonation Stabilization Vadose Zone Injection j or Agricultural Irrigation

Sulfuric Acid Antiscalant

MF Filtrate PS

Product PS

To Wells

Decarb

Ca t Cart Filters

RO

Lime

Typ. of 14

ConcentrateTo Residuals Sewer

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Expansion Project Description City is expanding the AWT Project Started in Mid 2008 Expansion Objectives: Expand MF/RO process to improve water quality for agricultural reuse. Increased RO Production Goal: 20 MGD permeate. Characterize Microconstituent and DBP Levels at AWT Treat if Necessary

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Basis of Antiscalant Study

g p g During Conceptual Design a Full Scale Test was Performed. Original Test Concept: Competition test of new antiscalant compounds. Was reduced sulfuric acid consumption feasible? Elevated phosphate levels p p limited performance of new antiscalant blends. Additional phosphorus removal was required for substantial operating pH changes changes.

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Antiscalant Study Test Plan Original Test Plan was Modified New Test Plan: Test rejection of microconstituents, DBPs and inorganics over a Broad pH Range. Required vendor selection prior to testing. Objective: Does rejection of small polar Obj i D j i f ll l compounds improve enough to warrant phosphorous removal?

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Antiscalant Study Membrane Selection

Use of Existing RO Equipment/Membranes Both RO trains use Fluid Systems TFC membrane. Side by Side test of New and Old Membrane: New Membrane: 1 year old at time of study Design Flux = 9.5 gfd Old Membrane 10 years old at time of study Design = 10.7 gfd

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Antiscalant Study Testing Plan

Stages: Incremental pH Stages (6.0, 6.3, 6.5, 6.7, 6.9, 7.2) Cleanings P f Cl i Performed d Between pH Stages: Low pH Pulses Attempted Acid and High pH Cleans Used

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Antiscalant Study Testing Plan

Testing Plan: Operate at each pH stage long enough to confirm capabilities of antiscalant. If scaling occurred, operate for long enough to stabilize operation and collect samples.

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Antiscalant Study Results Inorganic Ions

100%

99%

98%

97% Rejection

96%

95%

94%

93%

92% 6.00

6.20

6.40

6.60 pH

6.80

7.00

7.20

Old M b Membrane - N Na Old Membrane - Na

New M b N Membrane - N Na New Membrane - Na

Old M b Membranes - Cl Old Membrane - Cl

New M b N Membranes - Cl New Membrane - Cl

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Antiscalant Study Boron Results

50%

45%

40%

Rejection

35%

30%

25%

Conversion of boric acid to tetraborate

20% 6.00 6.20 6.40 6.60 pH New Membrane Old Membranes Linear (Old Membranes) Linear (New Membrane) 6.80 7.00 7.20

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Antiscalant Study Results Nitrosamines

95% 45%

90%

40%

Nitroso opyrrolidine and Nitro osomorpholine Rejection, %

85%

35%

80%

30%
NDMA Rejection % n,

75%

25%

70%

20%

65%

15%

60%

10%

55%

5%

50% 5.90

6.10

6.30

6.50 pH

6.70

6.90

7.10

0% 7.30

Old Membranes - Nitrosopyrrolidine New Membranes - NDMA Linear (Old Membranes - Ntirosmorpholine)

Old Membranes - Ntirosmorpholine Linear (Old Membranes - Nitrosopyrrolidine) Linear (New Membranes - NDMA)

* Low level (<15 ppt) NDMA data removed from trend, possible issues with sampling/testing

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Antiscalant Study CPC Results

Average Feed Concentration, ng/L
1

Compound Acetaminophen Caffeine Carbamazepine p Estradiol Estrone Ethynestradiol Fluoxetine Gemfibrozil Ibuprofen
1 1 1

Average Permeate 2 Concentration , ng/L 0.61 2.66 5.86

Average New Membrane Rejection, Rejection % 60.0% 63.0% 96.6%

Average Old Membrane Rejection, % 60.0% 62.0% 96.6%

1.3 6.1 146

Not Present in Feed Not Present in Feed Not Present in Feed 15.8 37.6 15.1 720.3
1

1.40 4.04 3.62 2.55 9.14

92.5% 90.9% 79.7% 99.7% Not Present in Feed 92.2% Not Present in Feed Not Present in Feed

91.9% 90.9% 82.0% 98.6% 92.2%

Meprobamate Progesterone Sulfamethoxazole Testosterone Triclosan Trimethoprim

1

99.3

12.9

0.75

95.1%

93.8%

(1) Average rejection calculation includes non-detect values estimated at the detection limit. (2) Average permeate concentration was estimated using non-detect values and is higher than permeate concentrations observed during testing.

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Testing Conclusions Operation at Increased pH was infeasible at the Water C W t Campus Incapable of meeting the new treatment p g objectives for NDMA at this facility. Additional upstream phosphorus removal required for pH > 6.5.

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Testing Conclusions Operation at higher solution pH produces better RO rejection. j ti Impact of future p changes on downstream p pH g process equipment must be considered. Applicable to many different applications for applications, example seawater and ultrapure water p production. In the future, membrane aging will be a key O&M consideration if facilities are tied to tighter DBP/Microconstituent requirements.

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Acknowledgements
y City of Scottsdale Art Nunez Binga Talabi SPI Wendy Broley Kevin Alexander Waterworks Engineers Malcolm Pirnie

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Thanks For Attending! g

Robert Buddy Boysen, PE Separation Processes, Inc.
950 W. Elliot Rd, Suite 112 Tempe, AZ 85284 480-302-3348 bboysen@spi-engineering.com

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